CORROSION AND ITS CONTROL

Introduction, Corrosion classification, Electrochemical theory with special reference to rusting of

iron. Galvanic series: need, characteristics, advantage. Factors affecting corrosion: Primary and
Secondary factors. Brief account of galvanic corrosion, pitting corrosion, intergranular corrosion
Brief account of stress corrosion, Corrosion control by material selection and proper design.
Corrosion control by use of inhibitors, Cathodic protection of metals, Anodic protection and metal
coating.
Learning Objectives:
1. Unfold the practical aspects of metal corrosion with real life examples.
2. Be able to describe the mechanism of corrosion by electrochemical theory
3. Describe different forms of corrosion- galvanic, pitting, inter-granular and stress
corrosion
4. Demonstrate an understanding of the importance of the factors affecting corrosion
5. Know about the different established and modern techniques to control corrosion such
as anodic/cathodic protection methods, organic /inorganic coatings
6. Distinguish between dry/wet corrosion, galvanizing/ tinning, electrochemical series/
galvanic series and organic/inorganic coating
1. INTRODUCTION
Various types of metals are used in residential and commercial structures, in bridges, in
automobiles, passenger trains, railroad, cars, ships, in pipelines and storage tanks. In addition,
metals are also used in various electronic applications such as printed circuit, computer discs,
connectors and switches. Metals also find use as coins of daily commerce, in jewellery, in
historical landmarks and in objects of arts. Some metals find application in human body as
replacements, as stents, as surgical plates, screws and wires. Whatever be the end use all common
metals, they tend to react with their environments to different extents and at different rates. Thus,
corrosion is a natural phenomenon, which is the destructive attack of a metal by its environment
results in weakening of the properties of the metal.
Corrosion can be defined as spontaneous destruction or deterioration of a metal or alloys
by the surrounding environment because of chemical or electrochemical interaction. Free metals,
as such are unstable and whenever favourable situation arises they combine with other elements
like oxygen and form the compounds of minimum energy and maximum stability. Hence corrosion

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can be viewed as the reverse process of extractive metallurgy. This phenomenon is schematically
represented in Figure 1

Figure 1: Corrosion as reversal of metallurgy

4Fe(s) + 3O2 (g) →2Fe2O3(s) (rust) , Fe2O3 (s) + 3 CO →2Fe(s) + 3 CO2 (g)
Three most common examples of corrosion include rusting of iron objects forming reddish
brown scale, tarnishing of silver in contact with traces of H2S or SO2 in the atmosphere or eggs
rich in sulfur compounds and formation of green scales on copper vessels. The process and the
products formed in these reactions are described in the following equations.
Rusting of iron 4Fe(s) + 3O2(g) → 2Fe2O3.H2O(s)
Tarnishing of silver 4Ag(s) +2 H2S(g) + O2(g) → 2Ag2S(s) + 2H2O(l)
Scales on copper 2Cu(s) + H2O(l) + O2(g) + CO2(g) →Cu2(OH)2CO3(s)

1.1 Importance of corrosion study

The study of corrosion is an interdisciplinary area embracing chemistry, material science and
mechanics. Four reasons to study corrosion as the science and engineering subjects are:
Human life and safety: Loss of life results due to combined effects of stress and corrosion when
structures collapse. Safety issue can be due to the build-up of certain toxic product due to corrosion,
sudden failure of equipment may cause fire or explosion.
Cost of corrosion: The annual losses due to corrosion are approximately 3-4% of GDP in many
advanced countries and it is even more in developing countries.
Conservation of materials: Corrosion destroys metals by converting them into corrosion
products. Thus corrosion affects the supply of the earth’s material resources.
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Academic interest: The study of corrosion is in itself a challenging and interesting as corrosion
science is an interdisciplinary area involving chemistry, materials science and mechanics. A blend
of these must be included to understand the various forms of corrosion.
1.2 Corrosion science versus corrosion engineering
Corrosion science is directed towards gaining basic scientific knowledge to understand
corrosion mechanisms. Corrosion engineering involves the use of accumulated scientific
knowledge to corrosion protection and prevention. Corrosion science and corrosion engineering
complement and reinforce each other. Understanding of corrosion mechanisms can lead to possible
new corrosion-resistant alloys, better surface treatments, and improved corrosion control
measures. Understanding of corrosion engineering aspects will trigger the interest in doing
research in finding out actual mechanisms involved in the process.
1.3 Consequences of corrosion
• Maintenance and operating costs: One fourth of the iron produced is used to replace
bridges, buildings and other structures that have been destroyed by corrosion. The
corrosion causes damage to chemical process plants and other equipment.
• Plant shutdowns, loss of production while the plant is inoperable during
repairs/replacement work.
• Contamination and loss of valuable products- Leaking containers, tanks, pipelines results
in significant losses in product, which have a high cost. Soluble corrosion products can
spoil and contaminate chemical preparations.
• Effects on safety- The contaminated products when dumped cause environmental pollution
problems.

2. CORROSION CLASSIFICATION
Two different types of corrosion are
* Dry or Chemical Corrosion and Wet or Electrochemical Corrosion
2.1 Dry or Chemical corrosion
This type of corrosion occurs by direct chemical reactions between the environment and
the metals and alloys. Presence of an electrolyte/conducting medium is not at all essential for this
type of corrosion to occur. Therefore this kind of corrosion is also known as dry corrosion.

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Depending upon the nature of the corrosive environment, dry corrosion may be further classified
into three types.
(i) Oxidation corrosion: It occurs when metals are attacked by dry oxygen (absence of moisture)
at extreme conditions like low or high temperature. The direct oxidation of metals takes place
according to the following reaction scheme:
2M → 2Mn+ + ne−
nO2 + 2ne− → 2nO2−
2M + nO2 → 2Mn+ 2nO2−
In general: Metal + Oxygen→ Metal oxide (corrosion product)
When the oxidation starts, a thin layer of oxide is formed on the metal surface. Nature of this film
decides the further corrosion process.
 If a stable film is formed, it behaves as protective coating and, thereby it shields the metal
surface from corrosive environment. Consequently, further oxidation of metal is prevented.
eg: Al, Sn, Pb, and Cu.
 Unstable metal film decomposes back into the metal and oxygen. Hence oxidation
corrosion is not possible in such cases: e.g. Ag, Au, and Pt.
 In some cases, oxide film layer volatilizes as soon as it is formed, thereby accelerating the
corrosion. e.g: MoO3.
(ii) Corrosion by other gases : It is due to some gases SO2, Cl2, CO2, and H2S, depends mainly on
the chemical affinity between the metal and the gas involved. For example, dry Cl 2 attacks silver
metal and forms AgCl as a thin protective and non-porous layer on the metal. As a result of this
protective layer on the metal surface, the intensity of corrosion decreases.
(iii) Liquid metal corrosion : It occurs when a molten liquid is continuously passed at high
tempeartures on a solid metal surface or on alloy. Such corrosion occur in devices used for nuclear
power. This behaviour may be either due to the dissolution of the molten liquid or due to
penetration of the molten liquid into the metal phase.
2.2 Wet or Electrochemical corrosion
Wet corrosion occurs due to the existence of separate anodic and catholic areas, between
which current flows through the conducting solution. It involves flow of electron current between
the anodic and cathodic areas through electronic conductor. This type of corrosion can be observed
when

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 (a) A metal is in contact with a conducting solution or
(b) Dissimilar metals or alloys are dipped partially in a corrosive medium.
2.2.1 Electrochemical theory of corrosion
Corrosion usually occurs not by direct chemical reaction of a metal with its
environment but rather through the operation of coupled electrochemical half-cell reaction.
According to electrochemical theory of corrosion, when a metal is exposed to corrosive
environment, the process of corrosion sets in by the formation of a large number of ‘anodic’ and
the ‘cathodic’ areas on the metal surface (microgalvanic cells). A driving force is necessary for
electrons to flow between the anodic areas to the cathodic areas. This driving force is the difference
in potential between anodic and cathodic areas. Corrosion always occurs at the ‘anodic area’ of the
metal due to oxidation process and thus electrons are liberated.
Anodic reaction:
M → Mn+ + ne−
Fe → Fe2+ + 2e−
Al → Al 3+ + 3e−
Cathodic reactions
The electrons set free at the anodic area flow through the medium and are consumed at the cathodic
area by following processes:
i) Hydrogen evolution:
2H+ (aq) + 2e− → H2 (deaerated and acidic medium)
(ii) H2 liberation along with OH− ions formation
2H2O + 2e− → H2 (g) + 2OH− (aq) (deaerated and neutral)
Reduction of oxygen in neutral medium:
(iii) O2 (aq) + 2H2O + 4e− → 4OH−(aq) (aerated and neutral)
In addition to the above mentioned cathodic reactions, following reactions may also occur at
cathodic region.
Oxygen reduction is the most common cathode reaction since any aqueous solution in
contact with air contains dissolved oxygen. Hydrogen evolution occurs in acidic media. Metal ion
reduction and metal deposition are rare. Schematic representation of the electrochemical theory of
corrosion is shown in Figure 2.

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 Figure 2: Schematic representation of electrochemical corrosion.
Figure 2 illustrates the four conditions which are necessary for electrochemical corrosion to occur.
These are: (i) An anodic reaction,
(ii) A cathodic reaction,
(iii) A metallic path of contact between anodic and cathodic sites (electronic
conduction)
(iv) A solution which contains dissolved ions capable of conducting a current
(electrolytic conduction)
From, electrochemical theory, it must be clear that no corrosion take place at the cathodic area
since cathodic reaction does not involve metal dissolution. Corrosion and hence metal dissolution
takes place only at the anodic area. Cathodic area stimulates corrosion of the anodic part by
utilizing the electrons produced at the anodic area.
2.2.2 Mechanism of rusting: Rusting is the name more commonly referred for the corrosion of
iron. When iron is exposed to an atmosphere, in the presence of moisture, it undergoes corrosion.
Depending upon the concentration of oxygen present in the environment different types of
corrosion products are produced. Figure 3 illustrates the rusting process of iron.

Figure 3: Schematic representation of rusting of iron

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At anodic area, iron undergoes oxidation and produces Fe2+, by liberating electrons. The liberated
electrons will migrate towards cathode causing corrosion current. The Fe2+ ions formed at the
anode combine with OH− liberated at the cathode to form the corrosion product (ferrous hydroxide)
somewhere between the anode and cathode, after diffusing towards each other through the
conducting medium.
At anodic sites; [Fe → Fe 2+ + 2e−] x 2
At cathodic sites; O2 (g) + 2H2O (l) + 4e− → 4OH−(aq)
Overall reaction; 2Fe + O2 (g) +2H2O (l) → 2Fe2+ (aq)+ 2OH−(aq)
Reactions to the formation of hydrated ferric oxide (rust)
Fe2+(aq) + 2OH− (aq) → Fe (OH)2
In the presence of enough oxygen, ferrous hydroxide reacts with moisture and oxygen to give
yellow rust.
4 Fe (OH)2 + 2 H2O + O2 → 2 [ Fe2O3. 3H2O] ( Yellow rust)
If the supply of oxygen is limited, the corrosion product may be black anhydrous magnetite.
6 Fe (OH)2 + O2 → 2 [ Fe3O4. 3H2O] ( Black Rust)
Rust is a brittle substance that easily flakes off the surface to expose more iron atoms, and the
process starts over again. It is too porous to shield the underlying metal from further oxidation.
2.2.3 Differences between dry corrosion and wet corrosion
Dry Corrosion Wet Corrosion
Involves direct attack of atmospheric Occurs due to the existence of separate anodic
gases and cathodic areas between which current
flows through the medium
Do not need a corrosive medium Needs corrosive medium
Types include oxidation corrosion, liquid Types include galvanic, pitting, stress and
metal corrosion and corrosion by gases intergranular
Less prevailing More common

3 GALVANIC SERIES
The galvanic series is an ordered listing of experimentally measured corrosion potentials of metals
and alloys in natural seawater. They are arranged in the order of their corrosion
tendencies/corrosion resistance.

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3.1 Need for galvanic series
1. In the electrochemical (EMF) series a metal high in the series is more anodic and undergoes
corrosion faster than the metal below it. For example, Li corrodes faster than Mg, Zn corrodes
faster than Fe and so on. However, some exceptions to this generalization are known. In Zn-
Al couple, Zn (below Al in the electrochemical series) is corroded; while aluminium acts as
cathodic is protected. These observations, exactly opposite to that predicted by the EMF series
are because metals like Al and Ti develop strongly adhering oxide layers on their surfaces.
The electrochemical series does not take passivity into account.
2. The electrochemical series does not account for corrosion behavior of alloys. The
electrochemical series lists Eo values of pure metals. But engineering applications involve
many alloys under various circumstances. Consequently, a more practical series called
galvanic series has been prepared by studying corrosion of metals and alloys in like sea water.
3.3 Characteristics of galvanic series.
• Galvanic series include both metals and alloys.
• Metals and alloys are arranged in the increasing order of their corrosion resistance in
seawater.
• Metals and alloys having almost same corrosion characteristics are grouped within a
square bracket.
• Same metal can occupy two positions in the galvanic series; For example, aluminium
occurs both active and noble region depending upon its active and passive states.
Figure 4 shows the schematic representation of the EMF Series and Galvanic series

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 Figure 4: The schematic representation of EMF Series and Galvanic series

3.4 Comparison between electrochemical and galvanic series

• In electrochemical series, electrode potentials are measured by dipping pure metals in their
salt solution of 1M concentration without any oxide film on it. The galvanic series was
developed by studying corrosion of metals and alloys in unpolluted sea water, without their
oxide films.
• The position of a given metal in electrochemical series is fixed based on the electrode
potential value. The position of a given metal may shift in galvanic series as it takes active
and passive states, irrespective of its electrode potential.
• Electrochemical series gives no information regarding the position of alloys. Alloys are
included in galvanic series based on their corrosion behavior

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 • In electrochemical series, metals and non- metals are included. In galvanic series, only
metals and alloys are included.

4. TYPES OF CORROSION

4.1 Galvanic corrosion

Galvanic corrosion occurs when two dissimilar metals are in physical contact in an
aqueous electrolyte. The less resistant metal acts as the anode (metal with lower electrode
potential) and the more resistant metal (metal with higher electrode potential) functions as the
cathode. Figure 5 depicts galvanic corrosion showing the anodic and cathodic regions and the
direction of electron flow.
Examples of galvanic corrosion include:

*copper piping connected to steel tanks.

* Zinc-coated screws in a sheet of copper,

*A stainless steel screw-in contact with cadmium plated steel washer.

* Steel propeller shaft in bronze bearing

Figure 5: (a) Galvanic Corrosion (b) Effects of Galvanic Corrosion

The severity of galvanic corrosion depends largely on the amount of moisture present. Corrosion
is greater in the coastal region than in a dry rural atmosphere. Condensate near a seashore contains
salt and therefore is more conductive (and corrosive) and a better electrolyte than condensate in an
inland location. Accelerated corrosion due to galvanic effects is usually more pronounced near the
junction with attack decreasing with increasing distance from that point. In the galvanic couple

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like Zn/Fe, Fe/Sn, Fe/Cu, Zn/Sn, Zn/Cu; the first metal is anodic with respect to the second metal
and hence undergoes corrosion. It is to be noted that nuts, bolts, and hinges are made up of one
single metal or alloy to prevent galvanic corrosion.
4.2 Pitting Corrosion

Pitting corrosion is a localized and intense form of corrosion and failure often occurs with
extreme suddenness without prior indication. In pitting corrosion, the pits are sometimes isolated
or close together that they look like a rough surface. Generally, a pit may be described as a cavity
or hole with a surface diameter about the same length as or less than the depth.
The important reasons for the pitting corrosion include
* Surface roughness or non-uniform finish.
* Scratches or cut edges.
* Local straining of metal due to non-uniform stress.
*Deposition of extraneous matter such as sand, scale, water drop, and dust
Whenever dust particles are deposited, owing to the different amounts of oxygen in contact, with
metal, the small part becomes the anodic area, and the surrounding large parts become the cathodic
area. Intense corrosion starts just underneath the impurity. Pitting corrosion is characterized by a
small anodic area and large cathodic area, resulting in accelerated corrosion at the anodic area.
Examples: peeling of tin coat on iron, deposition of dust, sand on the steel surface. The pitting
form of corrosion can be represented as shown in Figure 6.

Figure 6: (a) Pitting Corrosion (b) Effects of Pitting Corrosion.

Autocatalytic nature of pitting corrosion

This process is self-stimulating and self-propagating. The gravity effect is a direct result
of the autocatalytic nature of pitting. That is, the corrosion within a pit produces conditions that

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are both stimulating and necessary within a pit to produce conditions for the continuing activity of
the pit. It is illustrated in Figure 7.

Figure 7: (a) Autocatalytic nature of pits (b) Pitting corrosion in stainless steel

If metal is pitted by an aerated sodium chloride solution, rapid dissolution occurs within the pit,
while oxygen reduction takes place on the adjacent surface. The rapid dissolution of metal within
the pit tends to produce an excess of positive charge in this area, resulting in the migration of
chloride ions to maintain electro neutrality. Thus, in the pit there is a high concentration of metal
chloride and, as a result of hydrolysis, it forms a high concentration of hydrogen ions and
corresponding hydroxide. Both hydrogen and chloride ions stimulate the further dissolution of
metal and alloy and the entire process accelerates with time.
4.3 Inter-granular Corrosion

Intergranular corrosion refers to preferential corrosion along the grain boundaries in some
alloys. Grain boundaries are slightly more reactive than the bulk matrix under certain conditions.
A localized attack at and adjacent to grain boundaries takes place with relatively little corrosion of
grains. The alloy disintegrates and loses its strength. Inter-granular corrosion is caused due to the
deposition of impurities, enrichment of one of the alloying elements, or depletion of one of these
elements in the grain boundary areas. The grain boundaries contain material, which shows
electrode potential, more anodic than that of the grain center in the particular corroding medium.
Some of the examples of intergranular corrosion include are, small amounts of iron in
aluminum where the solubility of iron is low, which have been shown to segregate in the grain
boundaries and cause inter-granular corrosion. It has been observed that based on surface tension
consideration the zinc content of brass is higher at the grain boundaries. Depletion of chromium in
the grain boundary regions results in inter-granular corrosion of stainless steels.

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 Numerous failures of stainless steel have occurred because of intergranular corrosion.
The 18-8 stainless steels undergo intergranular corrosion when they are heated approximately in
the temperature range 265-419 °C. Carbon diffuses towards the grain boundary quite readily at
sensitizing temperatures, but chromium is much less mobile. The surface already available at the
grain boundary facilitates the formation of a new surface, namely that of the chromium carbide.
Due to the precipitation of chromium carbide at the grain boundaries, thereby just adjacent to grain
boundaries becomes depleted in chromium composition and is more anodic with respect to the
solid solution within the grain (which is richer in chromium). Hence the chromium-depleted zone
near the grain boundary is corroded because it does not contain sufficient corrosion resistance to
resist the attack in many corrosive environments and thus undergoes intergranular corrosion. This
situation is shown schematically in Figure 8.
Intergranular corrosion particularly in stainless steel and exfoliation in the aluminum alloy
is minimized by giving proper heat treatment and annealing process as well as using low carbon
grade steel.

Figure 8: Illustration for inter-granular corrosion

4.4 Stress Corrosion: Stress corrosion or cracking refers to cracking caused by the combined
effect of tensile stress (residual, applied or thermal) and a specific corrosive environment.
During stress corrosion/ cracking, the metal or alloy is virtually un-attacked over most of its
surface, while fine cracks progress through it. The two classic cases of stress corrosion cracking
are "season cracking" of brass cartridges (Figure 9) and caustic embrittlement of steel boilers.

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 Figure 9: Stress cracking of brass

The metal atoms under stress are at higher energy levels compared to those free from stress. The
stressed part of the metal becomes more reactive than the stress-free part. A corrosion cell is
formed with a stressed part acting as anode and the stress-free part serving as the cathode. The
stressed part undergoes corrosion under a specific corrosive environment, initiating the crack. It
grows and propagates through the metal until the metal failure occurs or it may stop after
propagating a finite distance when either the tensile stress or the corrosive environment is
eliminated. Thus the stress corrosion is characterized by three distinct steps of crack initiation,
crack propagation, and final failure. In the first step small crack forms at some point of high-stress
corrosion. Then crack propagation takes place as this crack advances incrementally with each
stress cycle. The final failure occurs very rapidly once the advancing crack has reached a critical
size.
The caustic embitterment is a typical example of stress corrosion. This is a dangerous
form of stress corrosion observed in the boiler. Water fed into boilers may contain free alkali.
Water softened by lime soda process contains sodium carbonate. Under high temperature and
pressure prevailing within boilers, sodium carbonate hydrolyses to sodium hydroxide and carbon
dioxide.
Na2CO3 (aq) + H2O (l) → 2NaOH + CO2(g)

Thus water inside the boiler becomes a very dilute NaOH solution. Local stresses exist in metal
sheets of the boiler under rivets. Minute cracks develop on the metal sheets when the stress is
relieved. Dilute NaOH solution flows into these minute hairline cracks. Water evaporates by the
heat of the metal, depositing sodium hydroxide within the cracks. Freshwater flows into them and

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evaporates again depositing more NaOH. The concentration of NaOH increases in these cracks
due to the repetition of this process. NaOH concentration cell forms between the stressed and
unstressed parts of the metal. The sodium hydroxide attacks the metal and forms sodium ferroate
(Na2FeO2) which further undergoes hydrolysis according to the following equation regenerating
NaOH.
Iron / Concentrated, Dilute / Iron

(stressed) NaOH (cracks) NaOH (unstressed) (boiler water)

ANODE CATHODE

3Na2FeO2 + 4 H2O → 6NaOH + Fe3O4 + H2

6Na2FeO2 + 6 H2O + O2 →12NaOH + 2Fe2O4

When iron changes to these oxides metallic properties like malleability and ductility are lost. It
becomes brittle. The brittleness is caused by caustic alkali. Hence it is called caustic embrittlement.
The minute hairline cracks are caused by local stresses under the rivet heads. The continuation of
caustic embrittlement of boiler parts often results in boiler failure, and extreme cases may lead to
a boiler explosion. The following methods can minimize the caustic embrittlement;
(i) Na2SO4, tannin, or lignin is added to the water. These substances deposit within the
cracks and prevent the infiltration and accumulation of NaOH.
(ii) The boiler can be constructed by welding the sheets to avoid local stresses.

(iii) Caustic embrittlement is minimized by using demineralized water that does not contain
NaOH and Na2CO3.

5 FACTORS AFFECTING CORROSION

The rate of corrosion of material in a given environment is influenced to a varying degree by

several factors. These factors can be classified into two types given below:
A) Primary factors – the factors associated mainly with the metal

B) Secondary factors – the factors which vary mostly with the environment

5.1 Primary factors

Factors related to corroding metals are known as primary factors.

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(a) Nature of metal and relative electrode potentials of metals

In general, metals with lower electrode potential values are more reactive than metals with higher
electrode potential values. However, there are few exceptions to this general trend, as some metals
show the property of passivity.
The magnitude of corrosion cell potential is one of the major factors which decide the
corrosion rate. The larger the potential difference between the anodic and cathodic region of the
corrosion cell, the higher is the corrosion rate, ie. more anodic metal undergoes corrosion to a
larger extent. When the potential difference is more, a higher corrosion current is produced. For
example; the corrosion of zinc is faster than iron when in contact with copper in a medium. This
is because the electrode potential difference between Zn and Cu is greater than that of Fe and Cu.
(b) Relative Cathodic and Anodic area
The rate of corrosion is greatly influenced by the relative areas of the anode and cathode. If a metal
has a small anodic area and a large cathodic area, then the corrosion is more intense and faster.
This is shown schematically in Figure 10(a). At the anode oxidation takes place, and electrons are
liberated. At the cathode, these electrons are consumed. When the anode is smaller, and the cathode
region is large all the electrons liberated at the anode are rapidly consumed at the cathode region.
The smaller anodic areas can meet the demand for electrons by the large cathodic areas by
undergoing corrosion at a faster rate. This makes the anodic reactions to take place at their
maximum rate thus increasing the corrosion rate. Example; Small steel pipe fitted in a large copper
tank; iron bolt and nuts in copper boilers.
If the cathode is smaller, the consumption of electrons will be slower, and the corrosion reaction
as a whole will be slower as shown schematically in Figure 10(b).

Figure 10. Schematic representation of the effect of the ratio of the anodic and
cathodic area

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(c)Hydrogen Overvoltage
The difference between the observed potential at which reduction of H+ ions to H2 gas occurs at a
cathode and the theoretical potential at which it should have occurred is known as hydrogen
overvoltage. The magnitude of hydrogen overvoltage depends upon the nature of the metal used
as the cathode. Increased hydrogen overvoltage at a cathode reduces the corrosion rate when the
reduction of H+ ions is the cathodic process. When the hydrogen overvoltage is low, H2 gas is
liberated easily, and then the cathodic reaction rate is faster. This makes the anodic response also
faster, thereby promoting overall corrosion reaction. On the other hand, if the hydrogen over-
voltage is higher, more difficult is the evolution of H2 gas at the cathode, thereby decreasing the
cathodic reaction rate and overall corrosion rate.

(d) Nature of corrosion product

The corrosion product is usually an oxide of the metal which may or may not form a protective
layer on the metallic surface. If the corrosion product deposits is insoluble, stable, uniform adherent
and nonporous, it acts as a protective film preventing the further corrosion of metal. e.g., the
formation of oxide film on the surface of aluminum, chromium, and titanium.
If the corrosion product is soluble, unstable, non-uniform, non-adherent and porous, the corrosion
continues unabated since in such cases fresh metal surface is continuously exposed to the corrosion
environment, and corrosion of the metal surface takes place continuously. e.g., Corrosion of iron
and zinc.
If the corrosion product is soluble in the corrosion medium or evaporates, then corrosion proceeds
at a faster rate as a fresh metal surface is exposed continuously to the corrosive environment, and
the destruction of the surface occurs continuously. e.g., Molybdenum oxide
If the corrosion product interacts with the medium to form another insoluble product, then a
protective film formed on the metal prevents further corrosion.e.g.PbSO4 formed in the case of Pb
in H2SO4.
5.2 Secondary factors
Factors related to the environment are known as secondary factors.

(a) Concentration and nature of electrolytes

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Rapid corrosion takes place at a high ionic concentration of the electrolyte due to an increase in its
conductivity. For example, the conductivity of deionized water is 1-10 millimhos per meter. The
conductivities of tap water and seawater are 10-20 milli-mhos per meter and 5.3 mhos per meter
respectively. Therefore, the corrosion rate in seawater is nearly 500 times as fast as that in tap
water and 5000 times as fast as that in demineralized water. In the marine atmosphere, the presence
of sodium and other chlorides leads to increased conductivity of the liquid layer in contact with
the metal surface, and thus corrosion rate is increased. The salt air of coastal cities is very
damaging to exposed metal when compared to that in interior places. In the vicinity of industrial
areas, the atmosphere contains corrosive gases like CO2, SO2, H2S, and fumes of HCl, and H2SO4.
So the acidity of the liquid adjacent to the metal surfaces increases and its electrical conductivity
also increases.
Similarly, some electrolytes can cause polarization and bring down the corrosion rate. The
phosphate ions form an insoluble, protective phosphate film of metal ions on the surface of a metal
and reduce its corrosion rate. The chloride ions penetrate the protective oxide film of metal
increasing the ionic conductance of the film. The protective action of this film decreases as a result
of this and the corrosion rate gets enhanced.
(a) pH of the medium

In general, the lower the pH of the corrosion medium, higher is the corrosion rate. The acidic media
provides a more conducive environment than the alkaline or neutral media. The corrosion rate
increases slowly and gradually with decreasing pH and become rapid at pH less than 4. At pH >
10, corrosion of iron practically ceases due to the formation of a protective coating of hydrated
oxides of iron. However, some metals like Al, Zn, and Pb, undergo fast corrosion in highly alkaline
solution.
(c) Temperature
The rate of a chemical reaction in general increases with the rise in temperature. Curve A of Figure
11 indicates the corrosion of Nickel in HCl. An increase in temperature increases the conductance
of the corrosion medium, which also contributes to the increase in corrosion rate. In the case of
corrosion-resistant passive metals, the rise in temperature decreases the passive range and thereby
increases the corrosion rate. However, in some cases, the initial negligible temperature effect will
be followed by a very rapid corrosion rate at a very high temperature. This trend is reflected in
Curve B of Figure 11. An example is the corrosion of stainless steel in HNO3. This is because

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increasing the temperature of nitric acid gently increases its oxidizing power. At low or moderate
temperatures, stainless steels exposed to nitric acid are in the passive state very close to the trans-
passive region. Hence at elevated temperature, there will be an increase in the oxidizing power of
the medium which increases the rate of corrosion. However, if the corrosion medium contains
dissolved gases, the solubility of the gases decreases with temperature. In such a situation corrosion
rate also decreases. The presence of too much humidity also reduces the rate of corrosion

Figure 11. Effect of temperature on the corrosion rate of A) Ni in HCl and B) stainless steel in
HNO3

(d) Polarization at the anodic and cathodic region

During electrochemical corrosion both anode and cathode can no longer be at their
reversible equilibrium potentials. The deviation from the reversible equilibrium potential of an
electrode when brought in contact with another electrode is called polarization. There is a variation
in electrode potential due to an inadequate supply of species from the bulk of the solution to the
electrode. In the process of corrosion, the polarization of an anode or cathode decreases the
corrosion rate substantially as anode and cathode polarization retards anode and cathode reactions
respectively. Because of anodic polarization (i.e., shifting of potential to more positive values and
the current to lower value), the tendency of the anodic metal surface to undergo oxidation
decreases. It slows down the anodic reaction and thus decreases the overall corrosion rate. Cathodic
polarization retards the cathodic reaction. This can be due to the chemical polarization of the
cathode reactant with an electron. The retarded movement of the cathodic reactant to the cathode
surface or retarded removal of the cathodic reaction product from the surface of the cathode also
makes the cathodic reaction slower. For the corrosion to continue both anodic and cathodic

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reactions should take place simultaneously. The slow rate of any one of the reactions makes the
corrosion reaction slower.

6. PROTECTION AGAINST CORROSION

Corrosion of metals occurs when they come in electrical contact with a corrosive
environment. Therefore metallic corrosion can be prevented by either changing the metal or
altering the environment or by separating the metal from the environment. However, the most
effective and economical method is to deal with the corrosion problem at the design stage itself.
Various methods available for corrosion control are discussed below.
6.1 Selection of materials and proper design
Selection of materials:- Planning for corrosion prevention starts with the selection of appropriate
metals and alloys. Therefore the following material selection principles need to be considered.
a) Noble metals such as Pt, Au, and Pd do not undergo corrosion. But noble metals are generally
not used because of its prohibitive price. Pure metals that show greater resistance to corrosion
than an impure one can be chosen.
b) The rate of corrosion can be controlled by using an anodic material of larger area and cathodic
material of smaller area.
c) Suitable alloying of metals in some cases improves its corrosion resistivity.
d) Avoid residual stress in fabricated articles by proper heat treatment (annealing).
e) The use of two dissimilar metals having large difference in their electrode potentials should be
avoided. Under unavoidable circumstances, the metals chosen should be very close in the
galvanic series. Proper insulator fitting may be used in between to prevent direct contact of
metals.
Proper design: - A good design minimizes corrosion in metallic structures or equipment. A large
number of corrosion failures are due to improper design and inability to use available knowledge.
Some general rules for design are described below:
a) Simplify forms: Structures having simpler forms can be protected easily and efficiently. A
complicated shape having more angles, corners, edges and internal surfaces will have a larger
surface area exposed to the corrosive environment and will be difficult to protect by painting or
other surface treatment. Improvement in design can be achieved through welding the joints as
shown in Figure 12.

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 Figure 12: Improvement of design by welding the joints
Electrical boxes exposed to the atmosphere should be so designed that water does not collect at
the top or in the crevices. The profile should be so designed that water is drained completely and
moisture retention should be as low as possible.
b) Avoid crevices: Crevices allow moisture and dirt to be trapped which result in increased
corrosion. If crevices are either present in a structure or cannot be avoided they should be filled
either by welding or by using fillers. (Figure 13)

Figure 13: Improved designs to minimize crevice corrosion

c) Avoid residual moisture: The design should be such as to protect the structure from residual
moisture; ventilation is usually as important as drainage (Figure 14).

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 Figure 14: Improved design to minimize differential aeration corrosion

d) Avoid sharp corners and bends: These are the potential corrosion sites, and round corners
must replace these. Sharp corners result in the thin coating at corners and are not protected
effectively. Rounding the corners can result in an even coating. Sharp bends and other areas where
the fluid directions change rapidly can promote corrosion and should be avoided (Figure 15).

Figure 15: Improved design with minimum sharp corners

6.2 Cathodic protection

Corrosion of a structure can be controlled if the entire article can be changed into the cathodic part
of a corrosion cell. This is called cathodic protection. Ship's steel hulls, offshore drilling platforms,
oil and gas undersea pipelines, containers used to store water and other liquids are protected by
this method.
Cathodic protection can be achieved by two different methods.
a) Sacrificial anode method b) Impressed current method
a) Sacrificial anode method
A more reactive metal is kept in contact with the metal structure to be protected as shown in Figure
16. The reactive metal becomes the anodic part, and the structure becomes the cathodic part of the
corrosion cell. As the anode is sacrificed to protect the structur, this method is called sacrificial
anode method.

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 Figure 16: Mg is used as the sacrificial anode for protecting the iron article
Mg is more reactive than iron, and hence is usually used as the anode in contact with iron. Following
reactions occur when Mg is made to couple with Iron.
Anode: 2Mg(s) → 2Mg2+ (aq) + 4e−
Cathode: O2 (g) + 2H2O (l) + 4e− → 4OH−(aq)
Net reaction: 2Mg(s) + O2(g) + 2H2O(l) → 2Mg(OH)2
Advantages:
* No external power supply is necessary.
* Can be used in remote and difficult to reach areas.
* Low installation cost.
* Minimum maintenance cost.
* Replacement of sacrificial anode is much cheaper than replacing the structure.
b) Impressed Current Method.
The metallic structure is made cathode with the use of impressed current by connecting the negative
terminal of the external DC power source to the metallic structure to be protected and positive to
an inert anode. The anode may be made up of steel, graphite or platinum group metals, which may
be consumed very slowly or may not be consumed at all depending on the anode material. If the
anode is a weak ionic conductor, it is surrounded by backfill consisting of coke breeze, gypsum to
improve electrical contact between the anode and the environment. Schematic representation of an
impressed method to control corrosion is shown in Figure 17.

Figure 17: Schematic diagram of an impressed current method

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Advantages:
* Applicable to large structures and long-term operations.
* Uncoated parts can be protected.
Disadvantages:
* Larger installation cost.
* Higher maintenance cost.
* High energy consumption
* Localized corrosion may occur if the impressed current is not uniform on the entire surface.
6.3 Anodic protection method
Anodic protection is based on the fact that under specific ranges of potentials a metal or alloy
becomes passive, resulting in the lowering or prevention of corrosion. The potential current density
diagram as shown in Figure 18 describes the anodic protection method.

Figure 18: Plot of Potential Vs. Corrosion current (corrosion rate).

Certain metals and alloys lose chemical reactivity under specific environmental conditions, which
is called passivity of metals. e.g., Al, Ti, Cr, Ni, Mo, and alloys containing a significant amount of
these metals. The curve in Figure 18 is obtained by applying a known potential to a metal specimen
and measuring the current changes. As the potential is increased, initially current also increases
(AB) indicating the dissolution of the metal. This trend continues until the current reaches a critical
value (Icrit) at an applied potential (Ecrit). Further, increase in potential leads to decrease in current
due to the development of oxide layer. At passivating potential (Ep), the current reaches a
minimum value called the passivating current ( Ip). The decrease in current is due to the formation

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of a passive film on the metal. If the potential is further increased the metal remains unattacked up
to a particular potential is reached (CD).In this range, the corrosion rate of the metal is minimal.The
potential range in which the anodic protection can be achieved is called the passive region. The
optimum potential for anodic protection is midway in the passive region since it permits slight
variations in the controlled potential without affecting the corrosion rate. Beyond the point D
(called trans-passive region) any further increase in potential tends to increase the current due to
the dissolution of metal.

Figure 19: Potentiostat used in anodic protection

The mechanism of protection thus lies in applying specific potential range in which no corrosion
takes place. This potential range depends primarily on the relationship between the metal and
reactants resulting in passivity. This technique protects Iron, Nickel, Chromium, Titanium and
their alloys. The anodic protection of a structure is applied by using a device called potentiostat. It
is an electronic device that maintains a constant potential with respect to a reference. The anodic
protection of steel tank containing sulphuric acid is shown in Figure 19.
Potentiostat has three terminals. One connected to the storage tank, other to an auxiliary cathode
(Pt) and third to a reference electrode (Calomel).In operation the potentiostat maintains a constant
potential between the tank and the reference electrode, corresponding to the passive range. The
potential is initially increased to Ep for the corrosion to occur, then increased to Ef (fade potential)
when the current decreases to a small value. Now the potential is kept at constant Ep, and the

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current is maintained at Ip. Example: Stainless steel containers used for transporting corrosive
chemicals are protected from corrosion by supporting them at proper Ef and Ip.
Advantages:
• Reduced equipment cost: possible to protect two or more vessels with one controller and
cost of anodic protection is generally independent of tank capacity.
• Applicable in extremely corrosive environments.
• Low current demand.
Disadvantages:
• Cannot be applied in corrosive medium containing aggressive anions such as chloride.
• Needs a continuous supply of electric current.
• Applicable only to those metals that show active-passive behaviour.
• Initial installation cost is high.
• Cannot reduce corrosion rate to zero.
6.4 Use of corrosion inhibitors
The use of corrosion inhibitors is a possible means of corrosion control by altering
the environment. A corrosion inhibitor is any chemical substance which when added to a corrosive
medium (usually in small amounts) increases the corrosion resistance. Corrosion inhibitors are
used in various industrial applications, including cooling water systems, automobile engine
coolants, acid pickling solutions, in the surface treatment of metals, in paints and organic coatings.
The mechanisms of corrosion inhibition are different for acidic and neutral solutions. In acid
solutions, natural oxide films initially present on the metal surface are dissolved away so that
inhibitors then interact directly with the metal surface. In neutral solutions, the system is more
complicated because the metal surface is oxide covered and also because dissolved oxygen may
participate in the electrode reaction. Many inhibitors protect against corrosion either by retarding
anodic dissolution process or cathodic reduction process or both the processes, and hence inhibitors
can be classified either as anodic or cathodic inhibitors.
a) Anodic Inhibitors: Substances used to stop the anodic reaction are called anodic inhibitors.
They form insoluble compounds with the metal ions formed at the anodic part due to its initial
corrosion. These insoluble compounds form a protective film on the anode surface, which
isolates the anode from the electrolyte medium and stops corrosion. The anions such as
chromate, tungstate, molybdate, and phosphate are used to arrest anodic processes. Anodic

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 inhibitors are found to be effective provided they are added above their critical concentrations.
If the added inhibitor is insufficient, it cannot plug all the anodic sites, which leads to severe
pitting corrosion.
b) Cathodic Inhibitors: Substances used to stop cathodic reaction are called cathodic inhibitors.
They form a protective film on the cathodic surface and isolate it from the electrolyte medium,
thereby stopping the cathodic reaction.
Two major reactions occur on the cathodic surface depending on the nature of the corrosive
environment: 1) Hydrogen evolution and 2) Oxygen absorption
1) Inhibitors that control hydrogen evolution reaction: 2H+ (aq)+ 2e- -------->H2(g) (acid medium)
The evolution of hydrogen gas over the cathode can be prevented either by retarding the diffusion
of H+ ions to the cathode or by increasing the hydrogen overvoltage. The diffusion of H+ to the
cathode is retarded by the addition of certain organic compounds which contain N or S. Urea,
thiourea, mercaptans and heterocyclic nitrogen compounds are widely used as cathodic inhibitors.
Such substances are adsorbed on the cathodic sites forming a protective film that suppresses
cathodic reaction. Even the use of insufficient concentration of these substances does not have any
adverse effect.
Increasing overvoltage of hydrogen can also prevent the evolution of H2 at the cathode. This is
achieved by the addition of oxides of Arsenic, Antimony or salts like sodium meta-arsenite. They
deposit as an adherent metallic film on the cathode areas thereby prevents the evolution of H2 since
hydrogen overvoltage for those metals is quite high.
2) Inhibitors that control Oxygen absorption: O2(g) + 2H2O (l) + 4e− → 4OH−(aq) (in neutral or
slightly alkaline medium)
This cathodic reaction can be easily controlled either by removing the oxygen from the corrosive
media or by decreasing the diffusion rate of oxygen to the cathode.
Reducing agents such as N2H4 and Na2SO3 remove oxygen from the corroding environment by
combining with it.
N2H4 + O2 → N2 + 2H2O
Decreasing the diffusion rate of oxygen is achieved by adding salts such as ZnSO4, MgSO4, NiSO4
to the aqueous environment. They undergo hydrolysis and form a deposit of their insoluble
hydroxide on the cathodic sites. The protective film being impermeable to oxygen prevents its
further diffusion to cathodic sites.

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 Zn2+ (aq) + 2OH− (aq) → Zn(OH)2.
6.5 Metal Coating
Coating of a metal on a metallic substrate requiring protection against corrosion is metallic coating.
There are two types of metallic coating.
* Anodic metal coating – coating the substrate metal with a more anodic metal, eg. galvanizing
* Cathodic metal coating - coating the substrate metal with a more cathodic metal, eg. Tinning
Galvanization:
Giving a Zn metal coating on iron and mild steel. When the coating covers the entire surface of the
substrate metal, the coating isolates it from the environment and protects it against corrosion. When
the coating breaks or cracks zinc act as the anode, and the substrate iron or mild steel acts as the
cathode. Thus zinc becomes the sacrificial anode and provides protection to iron or mild steel.

Figure 17. Galvanization process

Pretreatment: The metal surface is cleaned to remove organic matter like grease/oil by washing
with organic solvents. The rust and other deposits are removed by washing with dilute sulfuric
acid, and the surface is finally washed with water and air dried.
Process: Galvanization is done by hot dipping processes. Zn is melted (m.p: 419o C) and kept at
425-430o C. Ammonium chloride flux is spread over it to prevent its oxidation by air. Pretreated
iron or mild steel objects are then dipped in molten Zn bath. Pair of hot rollers wipes out the excess
of zinc coating to produce a thin uniform coating on the objects which are then cooled as shown
in Figure 17. Galvanized sheets cannot be used to prepare tins or cans for storing food materials,
because zinc salts are toxic.

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Applications: Used in the manufacture of fencing wire, roofing sheets, buckets, bolts, nuts, nails,
and screws.
Tinning:
A process involving a coating of tin on iron and mild steel is called tinning. Tinning protects the
article until the coating covers the surface thoroughly, by isolating it from the environment. When
the coating cracks, severe pitting corrosion of the articles at the exposed region occurs, because tin
is cathodic with iron and small anodic areas are in contact with the large cathodic area.
Pretreatment: Steel sheet is washed with organic solvents to remove grease/oil deposits. It is then
treated with dilute sulfuric acid to remove rust deposits and finally washed with water and air dried.
Process: Tinning is done by hot dipping. Tin is melted (232o C) and kept at 250o C. It is covered
with ZnCl2 and NH4Cl flux to protect liquid tin from oxidation by air. The petreated article is
dipped in molten tin, and passed through rollers kept in palm oil to squeeze out excess tin from it.
The sheet is cooled, rolled and stored as shown in Figure 20.

Figure 20: Tinning Process

Applications:
Used for coating steel, copper, and brass.
Used in the manufacture of containers for storing foodstuffs
For making cooking utensils and refrigeration equipment.
Comparison of Galvanizing and tinning
Galvanizing Tinning
A process of coating Zn over iron/ steel to A process of coating Sn over iron to prevent it
prevent it from rusting (anode metal coating) from corrosion (cathode metal coating)
Hot rollers used to wipe excess coat are not Hot rollers are immersed in oil
immersed in oil

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Galvanized containers cannot be used to store Tin coated containers can be used to store
acidic foodstuffs because zinc reacts with food foodstuffs because tin is nontoxic and does not
acids forming highly toxic zinc compounds. react to cause any food poisoning
Zn protects underlying iron by sacrificial action Sn protects iron due to its noble nature.
Zn continues to protect iron by sacrificial action Sn protects iron until the coating is perfect and
in the event of puncture/break in coating any break causes rapid corrosion of iron

7. SUMMARY
Corrosion is one of the problems often encountered in industrialized society, and its study is
important from the point of an engineering. Enormous breadths of engineering systems depend upon
corrosion protection for their reliability, performance, and safety. These corrosion problems are
typically complex phenomena, affected by many variables and not necessarily restricted to one form
of corrosion. The different types of corrosion include galvanic, pitting, inter-granular and stress
corrosion. Certain factors can tend to accelerate the action of a corrosion cell, and these include
nature of the metal and their relative environment, cathode and anode areas, nature of corrosion
products, hydrogen overvoltage, pH of the medium, temperature, and polarization. Various
measures are taken to control the corrosion rate, which include the selection of materials and proper
design, cathodic and anodic protection methods, surface coating and the use of corrosion inhibitors.
Review questions
1. Explain the meaning, importance, and consequences of corrosion in the industry and our
day-to-day lives.
2. Describe mechanism of rusting of iron.
3. Comment on the following statements, which can be either true or false.
(i) Al2O3 is corrosion resistant, but Fe2O3 promotes corrosion
(ii) A scratch formed on iron sheets coated with tin results in severe corrosion but the
case is the reverse when it is coated with zinc.
4. Explain the following terms as they apply to the corrosion; (a) Cathodic protection (b)
anodic protection.
5. Distinguish between dry and wet corrosion.
6. Explain the electrochemical theory of corrosion.
7. What are corrosion inhibitors? Explain the types of inhibitors used to control corrosion
with examples.

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8. Distinguish between the following; i) Electrochemical series and galvanic series ii)
Galvanizing and tinning.
9. Discuss the different factors affecting the corrosion process.
10. List the various methods used to control corrosion.
********

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